Scientific Inquiry and Review (SIR)

Volume 1, Issue 1, October 2017

ISSN (P): 2521-2427, ISSN (E): 2521-2435
Journal DOI: https://doi.org/10.29145/sir
Issue DOI: https://doi.org/10.29145/sir/11
Homepage: https://ssc.umt.edu.pk/sir/Home.aspx

Journal QR Code:

Article: DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro3

Compound: An Ab-Initio Investigation

Author(s): M. Rashid
M. A. Iqbal
N. A. Noor

Online Published: October 2017

Article DOI: 10.29145/sir/11/010104

Article QR Code:

To cite this article: Rashid M, Iqbal MA, Noor NA. DFT-Mbi of electronic and magnetic
properties of cubic cecro 3 compound: An Ab-Initio investigation. Sci
Inquiry Rev. 2017;1(1):27–36. DOI:
https://doi.org/10.29145/sir/11/010104

A publication of the
School of Science
University of Management and Technology
Lahore
 DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro Compound

DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro3

Compound: An Ab-Initio Investigation
Rashid, M1., Iqbal, M. A2. and Noor, N. A3*.
1
Department of Physics, COMSATS Institute of Information Technology,
Islamabad, Pakistan
2
Department of Physics, University of Management and Technology, Lahore,
Pakistan
*
naveedcssp@gmail.com
Abstract
By considering density functional theory (DFT) in terms of ab-initio investigation,
we have explored the structural, electronic and magnetic properties of cubic
CeCrO3 for the first time. In order to determine the structural stability of cubic
CeCrO3 compound, we optimized the structure of CeCrO3 in non-magnetic (NM),
ferromagnetic (FM) and Anti-ferromagnetic (AFM) phases by using PBE
generalized gradient approximation (GGA) functional to find the exchange-
correlation potential. From structural optimization, the FM phase of CeCrO3 is
observed to be stable. For computing electronic and magnetic properties, the
lately advanced modified Becke and Johnson local (spin) density approximation
(mBJLDA) is used. Calculated band structures and density of states plots with an
integer magnetic moment of 4 μB and reveal half-metallic character. In addition,
s–d exchange constants (N0α) and p–d exchange constant (N0β) are determined,
which are in agreement with a distinctive magneto-optical experiment.
Keywords: ab-initio calculations, cubic perovskite, half-metallic ferromagnetic,
magnetic properties
Introduction
Magneto-electric (ME) characteristic in the multi-ferroics, now a day’s has
become of vigorous importance, due to the existence of correlated ordering
parameter of electric and magnetic components that gets so much attention for
famous existing application such as sensor of magnetic field, memory elements
for multiple state, spintronic and multi-range microwave devices etc [1-3]. Detail
information of crystal and magnetic structure is matter of great concern for useful
application. Recently, the rare-earth ortho-ferrites have been reported like
GdFeO3 [5] and DyFeO3 [4] have been reported for ferro-electricity as well as
ME coupling effects. It is very difficult to perform polarization measurement
caused by high leakage current due to high Neel temperature of RFeO3
(TNFe=620–740K). At the same time as perovskite chromite RCrO3 exhibits
magnetic properties at lower TN values (110–280K).RCrO3 (R=Sm- Gd- Tb- Er-
Tm- and Y) [6,7] was reported to show signs of a fairly great electric polarization

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 Rashid, M., Iqbal, M. A et al.

(0.2–0.8μC/cm2), initially, at somewhat high temperatures equivalent to the TN of

the Cr sub-system. Additionally, LaCrO3, CeCrO3 have the maximum TN in
RCrO3 compounds, which is advantageous for device applications at room
temperature [8].
Perovskite oxides get so much attention due to its effective use in gas
separation membranes, solid fuel cell and piezoelectric etc. [9-14]. Lanthanide
doped perovskite type oxides, for example LnMeO3 (Ln: lanthanides, Me:
transition metals), have been accustomed for functional inorganic materials
having a inclusive diversity of applications for alkaline fuel cells electrodes [15],
gas ions sensors [16] and catalysts for fast and complete oxidation/reduction of
CO, NO and other hydrocarbons [17]. Various fascinating physical properties
such as structural, electronic, optical and magnetic properties are inter-dependent
in transition-metal oxides [18, 19]. These materials are predictable for spintronics
devices effectively.
The association of magnetic and electronic played a role to develop the
research in area of spintronics. Half-metallic ferromagnetism has a significant part
because of its spin- polarization at the Fermi-level which is necessary for the
better performance of spintronic applications [20, 21]. All these points force us to
explore half-metallic ferromagnets with important magnetic moment that well-
matched with existing semiconductor technology. Material similar to half-metal
have a unique property to act as conductor in one direction of spin and insulator
for opposite direction, therefore, it is very suitable for device applications and get
attention for researcher that are working in the area of spintronic devices [22-24].
Some major examples are magnetic disk drives, magnetic tunnel junctions,
magnetic hybrid technology for CMOS and magnetic sensor [25, 26], non-volatile
magnetic random access memories (MRAM) [27, 28]. By getting research
inspiration from de Groot et al. work, that explicate the insight of half-metallicity
to compute band structure using the half-Heusler alloys NiMnSb [29]. Several
research groups perform numerous experimental and computational studies on the
HM ferromagnets, and many HM materials have been predicted and experimental
verified [30].
CeCrO3 belongs to Pm-3m (No. 221) space group and have cubic crystal
structure. The atoms arrangement are as that Cr ions are placed at center of unit
cell and coordinated with 6 oxygen ions, Ce ions are distributed at the corner of
the cell and oxygen at center of the faces of unit cell. We have applied mBJ
scheme, as introduced by Becker and Johnson (BJ) [31], as it can properly find
electronic and magnetic characteristics. The structural properties of aforesaid
crystals are calculated at ground state and equated with the prevalent theoretical
and experimental data.

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 DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro Compound

2. Method of Calculations
In this study, predicted results were obtained by carrying the Density
Functional Theory (DFT), which is quantum mechanical approach that successful
in predicting fundamental properties of compounds and alloys in terms of
semiconducting trend. We employed DFT based full potential linearized
augmented plane wave plus local orbital (FP-LAPW+lo) method within the frame
work of Wien2K code [32]. In order to determine the ground state factors like
lattice constant and bulk modulus, we used generalized gradient approximation
(GGA) functional by considering the exchange-correlation potential suggested by
Perdew, Burke, and Ernzerhof (PBE) [33]. Whereas, recently developed modified
Becke-Johnson local density approximation functional (mBJLDA) [31] were used
to analyze the magnetic and electronic properties. The aim of using mBJLDA
potential for electronic properties is because of that exploring the improved
predicting bandgap as associated with standard LDA [34] or GGA [33].
In FP-LAPW+lo method, ion cores inside non-overlapping spheres and a
region of constant potential (interstitial region) are considered to the region
between the spheres. In interstitial region, a plane wave expansion is used,
whereas basis functions, potential and charge density were prolonged as
arrangements of spherical harmonic functions. The value of lmax=10 in muffin-
tin spheres for charge density and non-spherical potential was accomplished. For
energy merging, basis function expand upto RMT× Kmax =8 (in the plane wave
extension RMT represent the minimum sphere radius and KMAX the amount of the
largest K vector). A mesh of 56 k-points was used in the irreducible part of the
Brillouin zone (BZ) for structural, magnetic and electronic properties, which
certifies the convergence, are 3000 k-points. In addition, the charge density was
Fourier prolonged up to Gmax = 16. For cubic CeCrO3 perovskites, the RMT values
were elected to be 2.5, 1.72 and 1.87a.u. (atomic units) for Ce, Cr and O
correspondingly. For energy convergence, the calculations of self-consistent were
performed iteratively, when the total energy of the system is steady within 0.01
mRy.
3. Results and Discussion
3.1. Structural properties
To understand DFT based cubic CeCrO3, structure stability is check by
performing structural optimization in NM, FM and AFM phases. By using GGA-
PBE scheme, optimization is done by minimizing the total energy with reverence
to unit cell volume in each phase. From computed results (see Figure1), the total
energy difference between these two as ΔE =ENM – EFM and ΔE =EAFM – EFM. The
positive of ΔE confirmed that CeCrO3 is stable in FM phase (see Table 1). In
ABO3 oxides with B=Mn, Cr, Fe, Ni and Co, most of such oxides have FM

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 Rashid, M., Iqbal, M. A et al.

character. Similar, FM character is also proved in our study. Therefore, in first

step, we performed optimization in FM phase to compute the lattice constant a(Å)
and bulk modulus B for CeCrO3are shown in Table1.
The calculated tolerance factors for CeCrO3 are mentioned in Table1. Our
calculated value of tolerance factor is in adjacent covenant with the calculated
results [35, 36]. In cubic perovskite, the tolerance factor lies between 0.93 and
1.02 [36] and our measured values employed in this range, illuminating the cubic
structure of CeCrO3 compounds. The bond lengths are measured between various
atoms of the CeCrO3 and also listed in Table1. The tolerance factor can be
calculated using bond lengths by using the consequent formula:
0.707(< 𝐶𝑒 − 𝑂 >)
𝑡=
(< 𝐶𝑟 − 𝑂 >)

Figure1. The computed total minimum energy versus unit cell volume in
non-magnetic, ferro-magnetic and anti-ferromagnetic cubic CeCrO3 compound
Table1.
Calculated lattice parameters a(Å), Bulk moduli B(GPa), Tolerance factor, Bond
length, bandgap Eg (eV), Half-metallic EHM(eV), magnetic moments (µB) and
exchange constant parameters of FM cubic CeCrO3
Parameter CeCrO3
a0(Å) 3.877
B0(GPa) 183.81
Tolerance factor 0.999
Bond length Cr-O 1.9373
Bond length Ce-O 2.7397
Bond length Cr-Ce 3.355
Eg (eV) 2.89
EHM(eV) 0.38

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 DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro Compound

Total (µB) 4.0004

Cr (µB) 2.5283
Ce (µB) 0.9831
O (µB) 0.0642
Δx (d) 4.25
Δx (pd) 3.14
ΔEC (eV) 0.42
ΔEv ( eV) 2.70
Noα 0.33
Noβ 2.14
3.2. Electronic properties
Electronic band structure with mBJ DFT studies was discussed in this
electronic part. Energy eigen values obtained with the help of KS equation for
Electronic band structure. In the magnetic properties of CeCrO3 show match of
band structure due to spin up (↑) and down (↓) orientation of FM CeCrO3
polarized band structure in Figure2. In the analysis of spin-up state band structure,
it will be seen that the valance band (VB) maxima and conduction band (CB)
minima both found at point M of Brillion Zone (see in Figure2). For above
analysis, it is seen that up spin state of CeCrO3 demonstrate the FM
semiconductors behavior. The VB maxima cross the Fermi level (EF) for spin
down channel in CeCrO3, which describe the half-metallic manners is there for
spin down (↓) state. To disclose the starting point of density of states, partial
density of state for CeCrO3 is calculated and shown in the Figure3.

Figure2. The Calculated Spin Polarized Ferromagnetic Band Structures for Cubic
Cecro3 Compound with Mbj Potential

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 Rashid, M., Iqbal, M. A et al.

The (a) for majority spin (↑) and the (b) for minority spin (↓)
It understood able the Fermi level EF is cross for spin up, total DOS, on
the other hand the down channel form band gap at EF, resultant the charges make
a complete spin polarization and form this compound to utilize it for spintronics
devices. For compound CeCrO3 and by means of mBJ 2p states and 3d states of O
and Cr contributed primarily in the region of VB involving -4 eV to Fermi level.
If we deeply analyzed DOS from EF to 1 eV, we observed the 4f orbitals of Ce
contribution in DOS, after active over 3d states of Cr is clearly depicted. The shift
in these states to-words high energies and the contribution of 4f states of Ce
increments in the region of Fermi level clues to observed p-type conductivity and
100% spin polarization.

Figure3. The calculated (a) total density of states (DOS), along partial
DOS of (b) Ce, (c) Cr and (d) O by using mBJ for CeCrO3 compound.
3.3. Magnetic Properties
We obtained magnetic moment CeCrO3 from mBJ and listed in the
Table1. Although, the calculated value is to some extent lesser than the theory
value (µCr=2.52 μB). The fact of the smaller value is that the electrons in 3d are

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 DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro Compound

not totally confined but hybridized with oxygen of its 2p states. We have been
also calculated magnetic moments of Ce ions. From the calculation we suggest
that the total magnetic moment is predominantly because of Cr atoms and the ΜCe
may be negligible. The half metallic characteristic of materials is verified by the
numeral value of total magnetic moment. In our verdict the dual exchange method
is liable for ferromagnetism seen in CeCrO3 cubic perovskites and has indirect
exchange interface among transition metals and rare-earths by the mean of anion
O.
In addition splitting energy Δx(d) values of spin exchange that describes
the role of 3d states of transition metal in exchange method is studied for Cr, and
listed in the Table1. Most exciting calculated parameters from p-d and s-d
coupling are swap coefficients N0α, N0β, correspondingly [37], that decide the
swap interaction among TM d-state as well as charge carriers (holes and electrons
in the valance band and conduction band respectively). The swap coefficients
values for CeCrO3 are shown in Table1. Additional, the value of N0α has lower
than N0β indicate that the s-d contact at CB minima is greatly feebler than p-d
interaction at VB maxima, that may be evidence of ferromagnetic behavior
present in the given compound.
4. Conclusion
In conclusion, we have perceived structural, electronic and magnetic
properties of FM CeCrO3 compound by means of ab-initio calculations. To verify
the stability of CeCrO3 compound, we have optimized the structure in PM, FM
and AFM phases and have computed their total energy differences (ΔE1 and ΔE2).
The calculated value of ΔE1 and ΔE2 are positive, which confirm that CeCrO3 is
stable in FM phase. By analyzing band structure and density of state plots, we
find that CeCrO3 is a half-metallic ferromagnet, while predicted value of total
magnetic moments is 4 μB. In addition, Cr 3d (unfilled) state due to p-d
hybridization results in a fall of magnetic moment of Cr ions and identical of
magnetic moment in the Ce and O (nonmagnetic) ions. Furthermore, calculated
exchange constant N0α and N0β indicate a lower value of N0α than N0β, which
represents that spin-down state is more operative, due to p-d interaction at valance
band maxima and ferromagnetism is confirmed by their strong hybridization.
Furthermore, double-exchange mechanism is used to discuss the origin of the
ferromagnetism in CeCrO3.

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References
[1] Spaldin NA, Fiebig M. The renaissance of magnetoelectric multiferroics.
Science. 2005;309(5733):391–392.
[2] Fiebig M. Revival of the magnetoelectric effect. J Phys D Appl Phys.
2005;38(8):123–152.
[3] Khomskii D. Classifying multiferroics: mechanisms and effects. Physics.
2009;2(20):20–28.
[4] Tokunaga Y, Iguchi S, Arima T, Tokura Y. Magnetic-Field-Induced
Ferroelectric State in DyFeO3. Phys Rev Lett. 2008;101(9):097205–097210.
[5] Tokunaga Y, Furukawa N, Sakai H, Taguchi Y, Arima TH, Tokura Y.
Composite domain walls in a multiferroic perovskite ferrite. Nat Mater.
2009;8:558–562.
[6] Rajeswaran B, Khomskii DI, Zvezdin AK, Rao, CN, Sundaresan A. Field-
induced polar order at the Néel temperature of chromium in rare-earth
orthochromites: Interplay of rare-earth and Cr magnetism. Phys Rev B.
2012;86(21):214409–214415.
[7] Serrao CR, Kundu AK, Krupanidhi SB, Waghmare UV, Rao CN. Biferroic
YCrO3. Phys Rev. 2005;B72:220101–220108.
[8] Zhou JS, Alonso JA, Pomjakushin V, Goodenough, JB, Ren Y, Yan JQ, et
al. Intrinsic structural distortion and super exchange interaction in the
orthorhombic rare-earth perovskites RCrO3. Phys Rev B.
2010;81(21):214115–214120.
[9] Fong DD, Stephenson GB, Streiffer SK, Eastman JA, Auciello O, Fuoss
PH, et al. Ferroelectricity in ultrathin perovskite films. Science.
2004;304(5677):1650–1653.
[10] Petric A, Huang P, Tietz F, Evaluation of La–Sr–Co–Fe–O perovskites for
solid oxide fuel cells and gas separation membranes. Sol State Ion.
2000;135(1–4):719–725.
[11] Pena MA, Fierro JL. Chemical Structures and performance of Perovskite
Oxide. Chem Rev. 2000;101(7):1981–2017.
[12] Galasso FS. Perovskites and High Tc Superconductors. New York: Gordon
and Breach; 1990.
[13] Murtaza G, Ahmad I, Amin B, Afaq A, Maqbool M, Maqsood JK, et al.
Investigation of structural and optoelectronic properties of BaThO3. Opt
Mater. 2011;33(3):553–557.
[14] Hayatullah, Murtaza G, Khenata R, Mohammad S, Naeem S, Khalid MN, et
al. Structural, elastic, electronic and optical properties of CsMCl3 (M=Zn,
Cd). Physica B. 2013;420:15–23.

34
 DFT-Mbj Study of Electronic and Magnetic Properties of Cubic Cecro Compound

[15] Meadowcroft DB. Low-cost oxygen electrode material. Nature.

1970;226:847–848.
[16] Yang M, Huo L, Zhao H, Gao S, Rong Z. Electrical properties and Acetone-
Sensing characteristics of LaNi1–xTixO3 Perovskite System Prepared by
Amorphous Citrate Decomposition. Sens Actuators B Chem.
2009;143(1):111–118.
[17] Zhang HM, Shimizu Y, Teraoka Y, Miura N, Yamazoe N, Oxygen sorption
and catalytic properties of La1−xSrxCo1−yFeyO3 Perovskite-type oxides. J
Catal. 1990;121(2):432–440.
[18] Wong KM, Alay-e-Abbas SM, Shaukat A, Fang Y, Lei Y. First-principles
investigation of the size-dependent structural stability and electronic
properties of O-vacancies at the ZnO polar and non-polar surfaces. J Appl
Phys. 2013;113(1):014304.
[19] Wong KM, Alay-e-Abbas SM, Fang Y, Shaukat A, Lei Y. Spatial
distribution of neutral oxygen vacancies on ZnO nanowire surfaces: an
investigation combining confocal microscopy and first principles
calculations. J Appl Phys. 2013;114(3):034901.
[20] Wolf SA, Awschalom DD, Buhrman RA, Daughton JM, von-Molnar S,
Roukes ML, et al. Spintronics: a spin-based electronics vision for the future.
Science. 2001;294(5546):1488–95.
[21] Pickett WE, Moodera JS. Half metallic magnets. Phys Today. 2001;54:39.
[22] Saeed Y, Nazir S, Shaukat A, Reshak AH. Ab-initio calculations of Co-
based diluted magnetic semiconductors Cd1−xCoxX (X=S, Se, Te). J Magn
Magn Mater. 2010;322(20):3214–3222.
[23] Nazir S, Ikram N, Siddiqi SA, Saeed Y, Shaukat A, Reshak AH. First
principles density functional calculations of half-metallic ferromagnetism in
Zn1-xCrxS and Cd1-xCrxS. Curr Opin Solid State Mater Sci. 2010;14(1):1–
6.
[24] Saini HS, Singh M, Reshak AH, Kashyap MK. Emergence of half
metallicity in Cr-doped GaP dilute magnetic semiconductor compound
within solubility limit. J Alloy Compd. 2012;536:214–218.
[25] Wurmehl S, Fecher GH, Kandpal HC, Ksenofontov V, Felser C, Lin HJ.
Investigation of Co2FeSi: the Heusler compound with highest Curie
temperature and magnetic moment. Appl Phys Lett. 2006;88(3):032503.
[26] Wang W, Liu E, Kodzuka M, Sukegawa H, Wojcik M, Jedryka E, et al.
Coherent tunneling and giant tunneling magnetoresistance in
Co2FeAl/MgO/CoFe magnetic tunneling junctions. Phys Rev B.
2010;81(14):140402.

35
 Rashid, M., Iqbal, M. A et al.

[27] Zutic I, Fabian J, Das-Sarma S. Spintronics: fundamentals and applications.

Rev Mod Phys.2004;76(2):323.
[28] Karaca M, Kervan S, Kervan N. Half-metallic ferromagnetism in the CsSe
compound by density functional theory. J Alloy Compd. 2015;639:162–167.
[29] de Groot RA, Mueller FM, van Engen PD, Buschow KH. New Class of
Materials: Half-Metallic Ferromagnets. Phys Rev Lett. 1983;50(25):2024.
[30] Si C, Zhou J, Sun Z, Half-Metallic ferromagnetism and surface
functionalization-induced metal–insulator Transition in Graphene-like two-
dimensional Cr2C crystals. ACS Appl Mater Interfaces. 2015;7(31):17510–
17515.
[31] Tran F, Blaha P. Accurate band gaps of semiconductors and insulators with
a semi local exchange-correlation potential. Phys Rev Lett.
2009;102(22):226401.
[32] Blaha P, Schwarz K, Madsen G, Kvasnicka D, Luitz J. WIEN2K: An
augmented plane wave + local orbitals program for calculating
crystal propertie. Vienna, Austria: Vienna University of Technology; 2001.
[33] Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation
made simple. Phys Rev Lett. 1997;77:3865.
[34] Martin RM. Electronic structure: basic theory and practical methods.
Cambridge: Cambridge University Press; 2004.
[35] Kumar A, Verma AS, Bhardwaj SR. Prediction of Formability in
Perovskite-Type Oxides. The Open Applied Physics Journal. 2008;1:11–19.
[36] Xu N, Zhao H, Zhou X, Wei W, Lu X, Li F. Dependence of critical radius
of the cubic perovskite ABO 3 oxides on the radius of A- and B-site cations.
Int J Hydrog Energy. 2010;35:7295–7301.
[37] Sanvito S, Ordejon P, Hill NA. First-principles study of the origin and
nature of ferromagnetism in Ga1−xMnxAs. Phys Rev B.
2001;63(16):165206.

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